144863-72-9Relevant academic research and scientific papers
Z-Selective Hydrostannylation of Terminal and Internal C-C Triple Bonds Initiated by the Trityl Cation
Forster, Francis,Rendón López, Victoria M.,Oestreich, Martin
, p. 2656 - 2659 (2018)
A metal-free method for the anti-addition of n-Bu3SnH across terminal and internal alkynes, including related α,β-unsaturated carboxyl compounds, is reported. The reaction is initiated by the trityl salt [Ph3C]+[B(C6F5)4]- and proceeds through β-tin-stabilized vinyl cations. Their reduction by hydride transfer from n-Bu3SnH explains the high Z-selectivity in the formation of the vinyl stannanes.
Iron-Catalyzed Regiodivergent Hydrostannation of Alkynes: Intermediacy of Fe(IV)-H versus Fe(II)-Vinylidene
Liu, Jianguo,Song, Heng,Wang, Tianlin,Jia, Jiong,Tong, Qing-Xiao,Tung, Chen-Ho,Wang, Wenguang
supporting information, p. 409 - 419 (2021/01/12)
We report an iron system, Cp*Fe(1,2-R2PC6H4X), which controls the Markovnikov and anti-Markovnikov hydrostannation of alkynes by tuning the ionic metal-heteroatom bonds (Fe-X) reactivity. The sequential addition of nBu3SnH to the iron-amido catalyst (1, X = HN-, R = Ph) affords a distannyl Fe(IV)-H species responsible for syn-addition of the Sn-H bond across the CC bond to produce branched α-vinylstannanes. Activation of the C(sp)-H bond of alkynes by an iron-aryloxide catalyst (2, X = O-, R = Cy) affords an iron(II) vinylidene intermediate, allowing for gem-addition of the Sn-H to the terminal-carbon producing β-vinylstannanes. These catalytic reactions exhibit excellent regioselectivity and broad functional group compatibility and enable the large-scale synthesis of diverse vinylstannanes. Many new reactions have been established based on such a synthetic Fe-X platform to demonstrate that the initial step of the catalysis is conveniently controlled by the activation of either the tin hydride or the alkyne substrate.
